DE2134479A1 - Branched amide-imide-ester polymers for insulation varnishes - Google Patents

Description

Branched amide-imide-ester polymers for insulation varnishes

The invention relates to new branched amide-imide-ester polymers and their use as insulating varnishes for electrical Wires.

The representation of aromatic Araid imide reaction products of trimellitic anhydride and a diisocyanate is known from U.S. Patent 3,314,923 and the French. Patent 1,473,600 is known. Also the introduction of the trimellitic acid core in an imide polymer is described for Example in Belgian patent 6,50979 and in U.S. Pat. Patents 3,306,771, 3,238,181, 3,260,691 and 3,347,828. The use of dianhydrides to form polyimide resins is taught in U.S. Patents 3,190,856 and 3,179,634 described. The production of foams from trimellitic anhydride and diisocyanates is already in the U.S. Patents 3,072,614 and 3,300,420 are also described

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ist.die representation of polyester-polyimides from the U.S. Patents 3,426,098 and 3,425,866 are known.

However, none of the products described in these patents have all of the properties required for the manufacture of an insulation material. Although these products can withstand a heat shock test at 126.7 ° C, they are pre-stretched by $ 20 and still by. fit a 3X core, but they are only soluble in unusual solvents such as N-Methy1-2-pyrrolidone or dimethylformamide. There are drawbacks to the use of such solvents, not only in terms of their considerable cost when compared to solvents such as cresol. N-Methy1-2-pyrrolidone is extremely hygroscopic and dimethylformamide is also relatively hygroscopic. If these compounds are used as solvents for insulating varnishes for electrical * wires, the absorbed water increases the viscosity of the varnish extremely strongly. In order to eliminate this undesirable increase in viscosity, very careful processing and storage are required.

The branched amide-imide-ester varnishes of the present Invention are soluble in conventional solvents like cresol and they are not hygroscopic but rather can be stored indefinitely without increasing the viscosity. The polymers according to the invention are just "

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if more compatible with insulating varnishes than that common products of technology, in particular they are also compatible with alkyd insulating varnishes.

To solve the difficulties identified, it is proposed to produce amide-imide-ester polymers, to use these polymers as a coating material for electrical wires and furthermore a coating material to use for electrical wires, which gives these wires a good appearance, a stronger one Construction, better insulation properties and unusually good flexibility with heat and aging. It is also proposed to have electrical conductors with a coating with improved resistance to to provide higher temperatures and to produce coating material that has the properties mentioned and is still soluble in a common solvent such as cresol.

The desired properties can be obtained by reacting to form a prepolymer from trimellitic anhydride, an aromatic or alicyclic diamine and a trifunctional hydroxy compound and subsequent reaction of the prepolymer with a titanium-containing crosslinking agent and, possibly, a phenol-masked polyisocyanate.

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Methylene-dianiline or 4 »4'-diaminodiphenyl ether is preferably used as the aromatic diamine des.Prepolymer, but other aromatic diamines such as benzidine, 3» 3'-diamino-diphenyl, 1,4-diamino-naphthalene, can also be used. p-phenylenediamine, bis- (4-aminophenyl) - «\, ac ^l -p-xylene, m-phenylenediamine, diaminoxylene, hexamethylene diamine, 4,4 ^l -dicyclohexylmethanediamine or diamino -diphenylb sulfone.

The trimellitic anhydride can make up 100 $ of the acid anhydride portion of the prepolymer, but preferably up to 20 $ of the trimellitic anhydride is replaced by another dicarboxylic acid such as isophthalic acid, adipic acid, sebacic acid, phenylindanedicarboxylic acid or benzophenone-4,4'-dicarboxylic acid. In addition, it is desirable to add up to about 15 $ of the trimellitic anhydride ^ by benzophenone dianhydride, pyromellitic anhydride, benzophenone 2,3-2 ^f , 3 ^f -tetracarboxylic dianhydride, 2,3,6,7-naphthalene-tetracarboxylic dianhydride or 3 »3 ' -4 »4 ^l -diphenyl-tetracarboxylic dianhydride to. substitute.

As a trifunctional hydroxy compound of the prepolymer, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, Tris (2-hydroxyethyl) isocyanurate or trimethylol ethane can be used.

20981 1 / 176-6

Unless otherwise stated, all parts and percentages are by weight.

The proportion of diamine in the prepolymer is 33 to 43 equivalents per 100 parts, preferably

38.1 equivalents. The proportion of the anhydride and acid mixture in the prg polymer is 33 to 49 » 91 and preferably 47.7 equivalents per 100 parts. The following applies to the proportion of the trifunctional compound in the prepolymer: Palis 2-amino-2-ethyl-1,3-propanediol or 2-amino-2-methyl-1,3-propanediol can be used in the range of 3, 5 to 22 and preferably

14.2 equivalents are used if tris (ε-hydroxyethyl) isocyanurate or trimethylcurethane are used as trifunctional compounds, they can be used in the On the order of 3.3 to 18 and preferably 14.22 Equivalents are used per 100 parts.

It is necessary that an excess of amine and hydroxy compound remain in the prepolymer. The relationship from amine and hydroxy compound to anhydride and carboxyl groups is 1.05: 1 to 2.0sl and is preferably by 1.1: 1.

The isocyanate portion of the phenolically masked polyisocyanate can contain various polyisocyanates such as 4,4 ^l -diphenyl-methane-diisocyanate, 2,4-tolyl-

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diisocyanate, 2,6-tolyl diisocyanate, a mixture of 2,4- and 2,6-tolyl diisocyanates, m-phenylene diisocyanate, 1,6-hexamethylene diisocyanate, isopherone diisocyanate, the cyclic trimers of 2, 6-tolyl diisocyanate, the trimers of 2,4-tolyl diisocyanate, the trimers of a mixture of 2,6- and 2,4-tolyl diisocyanate, the trimer of 4,4 ^l -diphenyl meth.ane diisocyanate or the trimer of 1,3,5-triisocyanatobenzene.

Examples of crosslinking agents are Tetraiso-.propyl-eitanat, Tetramethyl-fiitanate, tetrabutyl-titanate, Tetrahexyl-Eitanat, Tetrapropyl-Sitanat, Triäthanolamin-Citanat, Titanium glycolate and tetratriethanolamine-fitan.

The proportion of the phenolic masked polyisocyanate can be determined as follows: For each 0.2 Excess equivalents of amine or hydroxyl groups in the prepolymer can be 0 to 1 and preferably 0.6 Equivalents of the phenolic blocked isocyanate are added. The titanium-containing crosslinking agent is in amounts from $ 0.1 to $ 12.5, and preferably $ 7 on the total amount of solids, (the total amount of solids consists of the weight of the prepolymer plus the weight of the isocyanate) used

The preparation of the prepolymer and the subsequent Reaction with the polyisocyanate is mostly

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carried out in the presence of the same solvent that is used to form the wire enamel. That preferred The solvent used is cresol, but other solvents can also be used, such as N-methyl-pyrrolidone, dimethylacetamide, dimethylformamide, Dimethyl sulfoxide, N-methyl-caprolactam, p-cresol, m-cresol, Mixtures of m- and p-cresol, dimethyl sulfone o.a. Mixtures of these solvents can also be used, such as mixtures of N-methylpyrrolidone and Dirnethylacetamide and / or dimethylformamide, mixtures from N-methyl-pyrrolidone, dirnethylacetamide and toluene (6: 3: 4) or N-ethyl-pyrrolidone and xylene.

Both aliphatic and aromatic hydrocarbons can be used as diluents are such as EW-Naphtha (wire enamel heavy oil tar naphtha), Solvesso No. 100, toluene, octane, decane, dodecane and tetradecane.

The branched amide-imide-ester polymers are

in solution as a coating agent for electrical wires

though
inserted, and>. . in the solvents listed above and preferably in cresol. The proportion of hydrocarbons in the solvent mixture can be between 0 and 40% by weight. The amount of amide-imide-ester polymer can be about $ 10 to $ 40 based on the total weight of the solution. Highly cross-linked thermosetting polyester or

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Polyester imides, as described, for example, in US Patents 3,342,780 and 3,426,098, are used to coat an electrical conductor such as a copper, silver, aluminum or stainless steel wire and then with the varnish according to the invention overdrawn. The lacquers can be applied to the electrical conductor by the usual methods such as dipping or spraying. A description of such coating methods is given in US Patent 3,201,276. The speed of the wire can be 45 to 180 m / min and the temperatures in the coating system can be from 138 ^° C. to 482 ^° C. In most cases, the final temperature is above 260 ⁰ C. By forming the base coat which consists of a highly cross-linked thermosetting polyester or polyester-imide, of 4,6yw.m -diameter takes the copper wire to four times the base coat by 50.8 to 52, 3M-Tue to. The paint of the invention is then applied over the crosslinked thermosetting base layers into two layers, is increased causing the diameter of the conductor by a further 10 to 25.4. The preferred increase in diameter is about 17 to 18 u.m.

example 1

To a solution of 192 g (1 mol) of trimellitic anhydride in 200 g of cresol, 158 g (0.8 mol) Methylenedianiline and 23 g (0.22 mol) 2-amino-2-methyl-1,3-propanediol admitted. This mixture was then based on

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2-13AA79

Heated 216 ⁰ C to 221 ⁰ C and maintained at that temperature, "until at a 20 $ strength by weight solids content in cresol a Z was formed to Z3 viscosity. The mixture was then diluted with 503 g of cresol and 293 g EW naphtha and to approximately The ^{mixture was then cooled to 55 °} C. 225 g of phenolically blocked 4,4'-diphenyl methane diisocyanate (prepared by adding 50 g (0.2 mol) of 4,4'-diphenyl methane diisocyanate to 175 g of cresol with subsequent heating added to 149 ⁰ C and subsequent cooling), the whole mixture was further cooled to about 49 ⁰ C and slowly 33 g of triethanolamine titanate (Tyzor TE) was added. the mixture was then reheated to 132 ⁰ C and left for 1 to 2 hours at this temperature. Then When the mixture was cooled again and diluted with 297 g of cresol and 97 g of EW naphtha, the reaction mixture now contained the calculated 20% solids and had a final viscosity of Z1.

The viscosities given relate to the Gardner-Holt scale, which can be found in "Paint, Varnishes, lacquers, and Colors "by Gardner and Sward, 12th Edition, 1962, pp 171-173.

Example 2

Methylene dianiline 158 g (0.8 mol) trimellitic anhydride 192 g (1.0 mol)

Tris (2-hydroxyethyl) -

ieocyanurate 52 g (0.2 mol)

p-cymene 20 g

Cresol _{Λ Λ} 100 g

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These ingredients were placed in a flask and heated to 227 ⁰ C. The reaction was continued until 34 ml of water had formed and had distilled off. Then 200 ml of cresol was slowly added to the reaction mixture. The mixture was then belas- to 216 ⁰ C abgekühl and was held at this temperature

until
sen, a further 2 ml of water were formed and distilled off. Then enough cresol was added that, together with the previously added amounts, 550 g of cresol were now present in the reaction mixture. Furthermore, 3Hg EW-Maphtha and 126 g N-Methy1-2-pyrrolidon were added. After the mixture had cooled to 121 ° C., 217 g of phenolically blocked 414'-diphenyl methane isocyanate were added. The blocked diisocyanate was obtained by adding 50 g of 4.4 ^? Multrsfhane the trademark M-diphenyl-methane-diisocyanate Mobay Co, made to 167 g of cresol, followed by heating to 99 ⁰ C in order to block the isocyanate groups. The temperature of the reaction mixture w was then lowered to 116 ⁰ C and slowly added to a solution of 12 g of triethanolamine titanate in 20 g cresol. The temperature of the mixture was then raised again to 121.1 ⁰ C and held for one hour. The product was then cooled and filtered. The final product contained a calculated solids content of $ 25 and had a viscosity of Z4 ⁺ .

Example 3

Methylenedianiline 158 g (0.8 mol)

Trimellitic anhydride 192 g (1.0 mol)

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-V-

,. "- ■ 213A479

Tris (2-hydroxyethyl) isocyanurate 52 g (0.2 mol) of cresol 100 g

The amounts indicated were introduced into a flask and heated to 238 ⁰ C. The reaction was continued at this temperature until 35 ml of water had formed and had distilled off. Then, 200 ml of cresol was slowly added to the reaction mixture and the mixture stirred at 221 ⁰ C left, was formed to a further ml of water and distilled off. Further cresol was then added to the reaction mixture up to a total cresol addition of 550 g. At the same time were 314 g EW naphtha and 126 g of N-methyl-2-pyrrolidone were added, 'The reaction mixture was cooled then "82.2 to ⁰ C, whereupon 50 g of 4,4 ^l - ^{1-diphenyl-diisocyanate} and 167 methaii g, which had been previously heated together to 99 ° C for blocking the isocyanate groups of cresol were added. the reaction mixture was further cooled to ⁰ to 64.4 C. and then mixed with 41,6g Titanglycolat (Tyzor OG). the mixture was then heated to 121.1 ⁰ C and maintained for two hours at this temperature. The reaction mixture was then from the calculated 25 # by weight solids content to a 20 # by weight solids by adding 284 g of cresol, 105 g EW naphtha and 31 g of N-methyl -2-pyrrolidone diluted.The end product had a viscosity of Z2 ~.

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Example 4

Methylenedianiline 158 g (0.8 mol)

Trimellitic anhydride 192 g (1.0 mol)

Tris (2-hydroxyethyl) isocyanurate 52 g (0.2 mol)

Cresol 100 g

The stated amounts were introduced into a flask and ^{heated to 238 °} C. and kept at this temperature until 34 ml of water had formed and had distilled off. Thereupon 200 ml of cresol were added and the mixture reheated to 221 ⁰ C, to v / urther 2 ml of water were formed and removed by distillation. Then cresol was added up to a total cresol content of 905 g as well as 159 g dimethylformamide and 382 g EW-naphtha. The mixture was cooled to 82.2 ⁰ C and then treated with 70 g of 40 $ strength by weight solution of the phenolic blocked trimers of toluene äiisocyanat in cresol was added. The mixture was further cooled to 49 ⁰ C and at this temperature 37 g of triethanolamine titanate (Tyzor TE) was added. The mixture was then ^{heated again to 123 °} C. and left at this temperature for 11/2 hours and then cooled. The resulting product had a calculated pesticide content of $ 20 and a viscosity of Y. 60 g of a 40% solution of the phenolically blocked trimer of toluene diisocyanate in cresol were then added, so that the end product had a viscosity of Y and a calculated pesticide content of 20 , Owned $ 3.

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Example 5

Methylenedianiline 158 g (0.8 mol)

Trimellitic anhydride '' 192 g (1.0MoI)

Tris (2 - ": hydroxyethyl) isocyanurate 52 g (0.2 mol)

Cresol 100 g

The stated amounts were placed in a flask, ^{heated to 232 °} C., left at this temperature until 34.5 ml of water had formed and had distilled off, and then 200 ml of Oresol were slowly added. The mixture was ^{heated to 218 °} C. and left at this temperature until 1.5 ml of water were further separated. Thereafter cresol was added to a Gesamtcresolanteil of 959 g and 337 EW naphtha added · The mixture was then cooled to 82.2 ⁰ C, with 150 g of a 40 weight solution of the phenolic # blocked trimer of toluene diisocyanate was added, further to 6O cooled ⁰ C and treated nit 37 g of triethanolamine titanate (Tyzor TE). The mixture was then reheated to 121.1 ⁰ C, kept at this temperature for 1 1/2 and then cooled. The end product had a calculated solids content of 22 »55 * and a viscosity from Z to 21.

Example 6

Methylenedianiline 158 g (0.8 mol)

Trimellitic anhydride. 192 g (1.0 mol) tris (2-hydroxyethyl) isocyanurate 52 g (0.2 mol)

^Creeo1 208811 / 1Ϊ66

Ir

These amounts were introduced into a flask heated to 232 ⁰ O and maintained at this temperature, were deposited to 34 ml of water. Thereupon 200 ml of cresol was added and the mixture stirred at 216 ⁰ G to the deposition of a further 2 ml of water was then left · cresol to a Gesamtcresolgehalt of 1130 g and 400 g EW-Haphtha added, the mixture cooled to 82.2 C ⁰ and 150 g of a 40% solution of a phenolically blocked trimer of tolyl diisocyanate in cresol are added. The mixture was further cooled to 60 ⁰ C and treated with 48 g of triethanolamine titanate (Tyzor TE). Subsequently, the mixture was again heated for 2 hours to 121.1 ⁰ C and then cooled. The final product had a calculated pesticide content of $ 20 and a viscosity of X '.

Example 7

Methylenedianiline 158 g (0.8 mol)

Trimellitic anhydride 173 g (0.9 mol)

Adipic acid 14 g (0.1 mol)

Tris (2-hydroxyethyl) isocyanurate 52 g (0.2 mol)

Cresol 100 g

These amounts were introduced into a flask and heated to 221 ⁰ C and up to a # 20 strength solids content in the cresol left at this temperature, a viscosity of Z2 to Z3 was created · Subsequently,

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797 g of cresol and 357 EW naphtha were added and the mixture was cooled to 54.4 ° C. Then 225 g of one became phenolic
"blocked 4,4'-diphenyl-methane-diisoeyanats (by heating at 138 ⁰ C to 1H9 ° C a mixture of 50 g
4.4 ^f -diphenyl methane diisocyanate prepared with 175 g of Gresol) was added, the mixture was further cooled to 49 ° C. and then 53 g of triethanolamine titanate (Tyzor TE) were added. The mixture was then reheated to 121.1 ⁰ C and left for 1 1/2 hours at this temperature and then cooled. The final product had a calculated solids content of $ 22.5 and a viscosity from Y to Z3.

Example 8

Methylenedianiline 158 g (0.8 mol)

j trimellitic anhydride 192 g (1.9 mol)

Trimethylolethane 27 g (0.22MoI)

Cresol ADF-14 200 g

II Cresol ADF-14 515 g

III EW-Kaphtha 295 g

IV Multrathane M.

Cresol ADF-14 ( ^{blocked at 138 0} C)

V Tyzor TE ($ 7 solids)

VI Cresol ADF-14

VII EW-Haphtha

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50 G (0, 2 moles) 150 G 33 G 397 G 97 G

I was ^{heated to 221 °} C. and left at this temperature until a viscosity of Z3 was reached with a 20% solids content. Then II and III were added and the mixture was ^{cooled to 60 °} C. and IV was added. The mixture was further cooled to ⁰ C and slowly added 54.4 V. Then, it was left for 1 1/2 hours at 132 ⁰ C again, then off at 93.3 ⁰ C. cools and mixed with YI and VII. After cooling, filter the mixture.

Example 9

The amide-imide ester polymers "from Example 1 were applied at a temper ature of 427 ⁰ C in a wire coating apparatus as a second protective layer over related with cross-linked thermosetting polyester copper wire. The speed of the wire in the coating system was in all cases 13 5 m / min. the length in U.S. Patent 3,249,578 cross-linked thermosetting polyester was described m so mounted in four layers on a copper wire having a diameter of 4.61 ^ that the diameter had increased to 58.3 mm. the amide Imide-ester polymers from Examples 1 to 8 were applied in two layers over the crosslinked, thermosetting polyester and increased the diameter by 18.5 μm. The coated wires produced in the conventional manner had the properties shown in Table 1.

To test the flexibility of the resulting

Film, the wire was abruptly stretched and then by one

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Core wrapped. In this winding, no cracks whatsoever must then occur in the E ¹ µm. To test for Schmorfestigkeit the wire is subjected to a load of 1000 V and 40 A at short notice, wherein the short term temperatures ranging from 300 ⁰ C to 50O ⁰ C may occur. The times required for the insulation varnish to dissolve and thus for the short circuit to occur provide information on the thermal resistance at briefly elevated temperatures.

To test the breakdown temperature, 1000 g of the wire are slowly heated in an oven and it is determined At what temperature the icing varnishes become thermoplastic and begin to flow · This gives an indication of the temperatures the wire can be exposed to over a long period of time without it deliquescing the coating lacquer short-circuit occurs.

In the heat shock test, a pre-stretched wire is briefly heated to a high temperature after it has previously been tight Turns of one's own diameter or a multiple of one's own diameter had been laid. Occurring Cracks and cracks in the insulation film provide information on the resistance of the paint to sudden stretching and sudden temperature changes

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ω Φ. Τ "· α> α » ι - * «» 4 σ » cn

Table 1

Example Appearance Flexibility test Braise resistance Through heat shock test

Core winding after drawing at 40 amps, 20 % pre-stretching. temperature for 1/2 h at 260 ⁰ O

2 3 4 5 6 7 8

Well 1x Well 2x Well 1X Well 2x Well 2x easily ge
waves
Il Il Il 2x
1x Il Il Il 2x

in ⁰ C 1χ 2χ 3χ 4χ 109 350 70 90 100 100 109 368 10 70 80 80 117 370 30th 60 90 100 152 361 30th 70 80 100 122 361 30th 80 90 80 124 360 30th 70 90 80 153 360 30th 90 1W) 1Ρ0 104 357 20th 90 70 90

Claims (6)

Claims 1. Amide-imide-ester polymer, which is essentially a Reaction product from (1) a-Amino-a-ethyl-lj ^ -propanediol, 2-amino-2-methyl-1,3-propanol, Tris (2-hydroxyethyl) isocyanurate or trimethylol ethane as a trifunctional hydroxy compound, (2) an aromatic or alicyclic diamine, (3) trimellitic anhydride or trimellitic anhydride with from fttschungen to 20Jß isophthalic acid, dicarboxylic acid V-adipic acid, sebacic acid, Phenylindandicarbonsaure, benzophenone ^ or with up to 15 $ benzophenone dianhydride, pyromellitic anhydride, benzophenone 2.3 to 2 ^1, 3 * -tetracarbonsäure- dianhydride, 2 »3i6j7-naphthalene-tetracarboxylic acid dianhydride or 3,3'-4,4'-diphenyl-tetracarboxylic acid anhydride as aromatic carboxylic acid anhydride, (4) a titanium-containing crosslinking agent and optionally (5) a phenolic blocked polyisocyanate. 209811/1765 -Hf- 2. amide-imide-ester polymer according to claim 1, characterized in that that the phenolically blocked polyisocyanate 4,4'-diphenyl methane diisocyanate, 2,4-tolyl diisocyanate, 2,6-tolyl diisocyanate, a mixture of 2,4- and 2,6-diisocyanate, m-phenylene diisocyanate, 1,3-hexamethylene diisocyanate, Isophorone diisocyanate, a cyclic trimer of 2,6-tolyl diisocyanate, a trimer of 2,4-tolyl diisocyanate, a mixture of the trimers of 2,6- and 2,4-tolyl diisocyanate or the trimer of 4,4'-diphenyl diisocyanate, and that the diamine hexamethylenediamine, 4-4 · - Are dicyclohexyl methanediamine or diamine diphenyl sulfone. 3. amide-imide-ester polymer according to claim 1, characterized in that that the proportion of diamine is 33 to 43 equivalent ^, the proportion of anhydrides and acids 33 to 47.5 equivalents ^, the proportion of the trifunctional hydroxy compound in the case of 2-amino-2-amino-2-ethyl-1,3-propanediol and 2-amino-2-methyl-1,3-propanediol 3.5 to 22 equivalents ^ and in the case of tris (2-hydroxyethyl) isocyanurates and trimethylolethane 3.3 to 18 equivalents ^ and that the ratio of the phenolically blocked polyisocyanate is 0 to 1 equivalents, based on 0.2 equivalents of excess amine in each case and hydroxy compound. 209811/1765 4. amide-imide-ester polymer according to claim 3, characterized in that that it is 0.1 to 12.5 # based on alkyl titanate the total weight of the polymer. 5. Amide-imide-ester polymer according to claim 1, characterized in that that there are 1 to 32 equivalents ^ excess amine and contains excess hydroxy compound. 6. Use of the polymer according to claim 1 to 5 together with an organic solvent, preferably cresol, and an alkyl titanate as an insulating varnish for electrical conductors. y. Use of the polymer according to claim 6 dissolved in a Solvent with a 60 to 100% content of cresol and a 0 to 40 # hydrocarbon content as an insulating varnish for electrical conductors. 209811/1765